Liquid detergent compositions



United States Patent LIQUID DETERGENT COMPOSITIONS Daniel A. Cook,Mentor Township, Lake County, Ohio, assignor to Diamond Alkali Company,Cleveland, Ohio,

a corporation "of Delaware This invention relates to a novel liquiddetergent composition, and more particularly relates to a new andimproved liquid detergent characterized by excellent cleansing power"and larity throughout a wide range of temperatures' and with water ofvarying "degrees of hardness.

Until fairly recently, general purpose detergents frequently have beensolid powders comprising mixtures of alkali andsoap adapted to bedissolved in water and applied as solutions. Various liquid organicsubstances, notably liquid non-ionic wettable agents, have demonstratedsuperiority in soil removal, sudsing ability and other desirableproperties and have been proposed as additives to powdered detergents.These liquids are, of course, limited inthe amount in which they can beincorporated into a powder or granular material without destroying itsparticulate nature. Moreover, dusting and caking of dry detergents arefrequently difficult to control so that considerable interest has beendirected toward liquid detergents. v

Liquid detergents have found application in a variety of washingandcleansing operations, e.g., in dishwashirig, windowwashing, handcleaning, machinery cleansing and a variety of applications in thedairy. industry in cleaning milking machines, inflations, utensils, milktanks, pipelines, milk cans, and the like.

' Prior liquid detergents 'comprising a major portion of liquidnon-ionicadditives, or a mixture of non-ionic and anionic surface activeagents have not been completely satisfactory. Anionic materials alonefrequently do not provide desirable results in hard water. On the otherhand, it has been found that a liquid non-ionic substance lay itselfdoes not provide an entirely satisfactory material, notably because of adisadvantageous cloud point. Accordingly, there has been a continuinginterest in seeking new and improved liquid detergents.

Accordingly, it is a principal object of the present invention toprovide a new and improved general purpose liquid; detergent whichavoids the difiiculties heretofore encountered.

A further object of this invention is to'provide a new and improvedliquid detergent which is characterized by a desirable viscosity, color,film characteristics, hard water resistance, cold weather properties andexcellent detergency.

These and other objects and advantages of the present invention willappear more fully from the following description-thereof,

The present invention contemplates a liquid detergent compositioncomprising 'in admixture the following ingiedients: J

.l l Parts (21) Alkyl-arylsul-fonate- (100% active) a 6-9 (b) Alkyl arylpolyether alcohol (100% active) 23-26 (0) At least one substanceselected from the group consisting of:

"ice

A liquid detergent composition of the above type is found to have adesirable viscosity and yet is not thick enough to cause difliculty inpouring nor is it subject to freezing at any typically-encountered lowtemperature. Further, a liquid detergent of the above composition has adesirable color, excellent sudsing characteristics, and is characterizedby clarity and an absence of cloud point up to C. and an excellent hardwater resistance whereby clear solutions are provided in water havinghardness values ranging from 10-100 grains or more.

The expression alkyl aryl sulfonate as used throughout the specificationand claims is intended, of course, to refer to various alkyl arylsulfonates and their alkali metal salts such as sodium salts, potassiumsalts, andthe like. Preferred alkyl aryl sulfonates are alkyl benzene,toluene, and/or naphthalene sulfonates where the alkyl group containsfrom about 4 to 18, preferably 10-14, carbon atoms, e. g., sodiumdodecyl aryl derivatives derived from propylene tetramer or kerosenefractions (keryl) averaging 12 carbon atoms. A specific preferred alkylaryl sulfonate is sodium dodecyl benzene sulfonate. Such a material isavailable commercially as Ultra-Wet 35 KX which typically comprises anaqueous solution of 68% by weight water and 32% by weight sodiumdodecylbenzene sulfonate.

The expression alkyl aryl polyether alcohol as used throughout thespecification and claims is intended, of course, to refer to variousalkyl aryl polyether alkanols,

, notably ethanol, such as alkyl benzene polyoxyethylene hydroxidesThese compounds can be prepared by constituent isocyclicw hydroxycompounds having as a substituent in the nucleus at least onehydrocarbon or acyclic radical of at least 4 carbon atoms, withethyleneoxide. Suitable isocyclic compounds are normal butyl phenol, 'diisobutylphenol, dodecyl phenol, and the like. The condensation can be carriedout at an elevated temperature in the presence of an alkali. Forexample, 206 parts by weight of p-isooctyl phenol are melted andcombined with 2 parts by weight of a 40% caustic soda solution. To thismixture there is introduced ethylene oxide at 130 C. until a total of 10molecules have been adsorbed for each molecule of the phenol. Acommercially available product of this type is Triton X-lOO.

The term alkanolamide as used throughout the specification and claims isintended to refer to various alkanolamides, especially monoanddialkanolamides such as monoand diethanolamides, dimethanolamides,ethanol-' amides, methanolamides, and the like, although adiethanolamide is preferred at present, such as the commerciallyavailable product as Solar CO which is obtained by reacting coconutzoilwith diethanolamine and typically comprises a mixture of 72% by weightdiethanolamide, 1% by weight diethanolamine laurate, 21% by weightdiethanolamine and 6% by weight glycerine.

The expression polyoxyalkylene alkanol, as used throughout thespecification and claims, is intended to refer to various compounds ofthis type, especially polyoxyalkylene ethanols. An illustrative andpreferred polyalkylene ethanol compound is tridecyl polyoxyethyleneethanol. A commercially available material of this type is the productknown as Emulphor BC-840 which is a liquid, 100% active polyoxyalkyleneethanol.

The term antifreeze as used throughout the specifi- I cation and claimsgenerally refers to organic compounds which may be added to preventfreezing of the liquid detergent composition. At present, it ispreferred to employ a mixture of antifreeze compounds, notably a mixtureof about equal proportions of (1) an alkylene glycol such as hexyleneglycol and (2) an'alkanol such as methanol, ethanol, or the like. Itwill be appreciated, of course, that in certain instances,antifreeze'compounds need not be added whenthe intended application doesnot involve exposure to freezing temperatures.

The term sequestrant, as used throughout the specification and claims,is intended to refer to additives capable of preventing sludge formationin hard water or other undesirable clouding. A preferred type ofSequestrant at present is the commercially available material known asSequesterene or Nullapon, which istetrasodium salt of ethylene diaminetetra-acetic acid. Other polyamino polycarboxylic acids, salts andderivatives thereof, as well as difierent compatible sequestrants, alsomay be used.

Liquid detergents embodying the present invention can be prepared bymixing the specified ingredients in the indicated amounts. Theproportion ranges specified are critical and should be mentioned if theadvantageous results characterizing the practice of this invention areto be obtained.

In order that those skilled in the art may more completely understandthe present invention and the preferred methods by which the same may becarried into effect, the following specific examples are offered:

Example I An illustrative liquid detergent in accordance with thepresent invention is as follows:

Percent by weight Alkyl aryl sulfonate (32% active) Ultrawet 35 KX 25.0(8.0% active) Alkyl aryl polyether alcohol (100% active) TritonPolyoxyalkalene alkanol (100% active) Emulphor Hexylene glycol Ethanol(denatured) 3.0 Sequestrant (Sequestrene) 0.1 Water Balance Example 11Another illustrative liquid detergent formulation in accordance with thepresent invention is the following: Percent by weight Alkyl arylsulfonate (32% active) Ultrawet 35 KX 21.7 (7.0% active) Alkyl arylpolyether alcohol (100% active) Triton 0 25.0 Alkanolamide (72%diethanolamide)-Solar CO 5.0 Hexylene glycol 3.0 Ethanol (denatured) 3.0Sequestrant (Sequestrene) 0.1 Water Balance It is to be understood thatalthough the invention has been described with specific reference toparticular embodiments thereof, it'is not to be so limited, sincechanges and alterations therein may be made which are -withini 4 thefull intended scope of this invention as defined b the appended claims.

What is claimed is:

1. A liquid detergent composition characterized by a high degree ofclarity and absence of a cloud point up to C. and capable of providingclear solutions in water having hardness values ranging from 10 to 100grains, said detergent comprising in admixture the followingingredients:

Percent by weight.

2. A liquid detergent composition characterized by a= high degree ofclarity and absence of a cloudpoint up to 100 C. and capable ofproviding clear solutions in Water having hardness values ranging'from10 to 100 grains, said detergent comprising in admixture the followingingredients:

' Percent: by weight (a) Sodium dodecyl benzene sulfonate 7.

(b) Alkyl benzene polyether ethanol 25 (c) Diethanolamide mixtureconsisting essentially of 72% by weight diethanolamide, 1% by weightdiethanolamine laurate, 21% by weight diethanolamine, and 6% by weightglycerine 5 (a') Hexylene glycol 3. (e) Ethanol 3' (f) Tetrasodium saltof ethylene diamine tetra-acetic acid 0:1 Balance 3. A liquid detergentcomposition characterized by a high degree of clarity and absence of acloud pointup to 100 C. and capable of providing clear solutions'in.water having hardness values ranging from' 10 to 100. grains,said'detergent comprising in admixture the follow-' ing ingredients:

Percent by weight (a) Sodium dodecyl benzene sulfonate 8. (b) Alkylbenzene polyether ethanol 24 (c) Tridecylpolyoxyethylene alcohol 5 (d)Hexylene glycol 3 (e) Ethyl alcohol 3:

(f) Tetrasodium salt of ethylene diamine tetra-acetic acid (g) WaterReferences Cited in the file of this patent UNITED STATES PATENTS Vitaleet al. June- 15, 1954 Bloch et al Sept. 6,,1955' Epstein et al. Jan. 31,1956 OTHER REFERENCESv Hexylene Glycol, Tech. Booklet SC: 50-1, 19.50.Shell- Chem. Corp., N.Y., pp. 8, 9 and 21.

Sequestrene, pub. of Geigy Ind. Chem., N.Y., 1952, pp. 42 and 43. j

0.1 Balance UNITED STATES PATENT OFFICE CETlFICATE OF CORECTION PatentNor, 2343 058 June 28 1960 Daniel Cook It is hereby certified that errorappears in the-printed specification of the above numbered patentrequiring correction and that the said Letters Patent should read ascorrected below.

Column 1 line 18 for "larity" read clarity line 25 for "wettable" readwetting =3 column 2, lines 36 and 37 for "constituent" read condensing=-=g line 58,, after product insert known =3 same column 2 line 66 for"p0ly=" read polyoxy column 4 line l4; at the end of the line underPercent by weight insert we 5 same column 4 lines 20 and 21 at the endof the line under Per cent by weightm strike out they-numerals "5% eachoccurrence,

Signed and sealed this 3rd day of January 1961.,

(SEAL) Attest:

KARL H, AXLINE ROBERT C. WATSON Attesting Ofilcer Commissioner ofPatents

1. A LIQUID DETERGENT COMPOSITION CHARACTERIZED BY A HIGH DEGREE OFCLARITY AND ABSENCE OF A CLOUD POINT UP TO 100*C. AND CAPABLE OFPROVIDING CLEAR SOLUTIONS IN WATER HAVING HARDNESS VALUES RANGING FROM10 TO 100 GRAINS, SAID DETERGENT COMPRISING IN ADMIXTURE THE FOLLOWINGINGREDIENTS: PERCENT BY WEIGHT (A) SODIUM DODECYL BENZENE SULFONATE------ 7-8 (B) ALKYL BENZENE POLYETHER ETHANOL ------- 24-25 (C) ATLEAST ONE SUBSTANCE SELECTED FROM THE GROUP CONSISTING OF: (1)DIETHANOLAMIDE MIXTURE CONSISTING ESSENTIALLY OF 72% BY WEIGHTDIETHANOLAMIDE, 1% BY WEIGHT DIETHANOLAMINE LAURATE, 21% BY WEIGHTDIETHANOLAMINE, AND 6% BY WEIGHT GLYCERINE ----------------------- 5 (2)TRIDECYL POLYOXYETHYLENE ALCOHOL ---- 5 (D) HEXYLENE GLYCOL----------------------- 3 (E) ETHYL ALCOHOL ------------------------- 3(F) TETRASODIUM SALT OF ETHYLENE DIAMINE TETRAACETIC ACID------------------------------ 0.1 (G) WATER--------------------------------- BALANCE